CN106467559A - Fire retardant dimethyl silicic acid disulfide group phospha trioxa cage ring octyl group methyl compound and preparation method thereof - Google Patents
Fire retardant dimethyl silicic acid disulfide group phospha trioxa cage ring octyl group methyl compound and preparation method thereof Download PDFInfo
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- CN106467559A CN106467559A CN201610850678.8A CN201610850678A CN106467559A CN 106467559 A CN106467559 A CN 106467559A CN 201610850678 A CN201610850678 A CN 201610850678A CN 106467559 A CN106467559 A CN 106467559A
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- trioxa
- phosphabicyclos
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The present invention relates to double 1 sulfenyl phospha, 2,6,7 trioxa-l-phosphabicyclo [2.2.2] octyl group 4 methyl compound of a kind of fire retardant dimethyl silicic acid and preparation method thereof, the structure of this compound is shown below：Preparation method is：1 sulfenyl phospha 4 methylol 2,6,7 trioxa-l-phosphabicyclos [2.2.2] octane and dimethylformamide dimethyl oxosilane, at 80 DEG C～100 DEG C, fractional distillation reacts 5h～9h or in organic solvent, 1 sulfenyl phospha 4 methylol 2,6,7 trioxa-l-phosphabicyclos [2.2.2] octane and dimethyldichlorosilane, react 5h～10h at 40 DEG C～80 DEG C；Purified process to obtain double 1 sulfenyl phospha, 2,6,7 trioxa-l-phosphabicyclo [2.2.2] octyl group 4 methyl ester of dimethyl silicic acid.Fire retardant efficiency of the present invention is high, becomes charcoal effect good, is suitable as the fire-retardant carbon forming agent of polyester, polyurethane, epoxy resin, unsaturated-resin etc., and simple production process, low cost, it is easy to accomplish industrialized production.
Description
Technical field
The present invention relates to a kind of double -1- sulfenyl phospha -2 of silicon, phosphorus, sulphur element synergistic fire retardant dimethyl silicic acid, 6,7-
Trioxa-l-phosphabicyclo [2.2.2] octyl group -4- methyl compound and preparation method thereof, this compound is suitable as polyester, polyurethane, ring
The fire-retardant carbon forming agent of oxygen tree fat, unsaturated-resin etc..
Background technology
The invention of fire retardant has made very big contribution with application to mankind's Reduction of Fire Disaster.In the today focusing on ecological protection,
People put forward higher requirement to fire retardant, and halogen-free flame retardants has obtained rapid development.Phosphorus flame retardant is to study now
More fire retardant, it is also proposed more perfect fire-retardant theory simultaneously.But, there is decomposition temperature in most of phosphorus flame retardants
Low it is impossible to adapt to macromolecular material high temperature process shortcoming.Because the cage circulus in cage phosphorus compound is steady to compound
Qualitative have certain contribution so as to have higher decomposition temperature, and most of cage phosphorus is with polyhydroxy-alcohol as skeleton, intramolecular
Integrate acid source and carbon source, there is good one-tenth charcoal anti-drip performance.Silicon-series five-retardant is instantly to study hotter fire retardant,
Element silicon has good one-tenth charcoal, when wherein containing C-Si, becomes charcoal more excellent.Therefore, research has above-mentioned advantage
Si-P synergistic fire retardant has theoretical well and using value.
The invention discloses with dimethyldimethoxysil,ne or dimethyldichlorosilane, 1- sulfenyl phospha -4- methylol -
2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane prepares silicon, phosphorus, sulphur element synergistic fire retardant dimethyl silicic acid for primary raw material
Double -1- sulfenyl phospha -2, the method for 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl compound.Fire retardant of the present invention has
Multiple fire retardant mechanism, wherein P elements can generate polyphosphoric acid film in burning, block combustible and air；Element silicon can generate cause
Close silicon layer of charcoal；Element sulphur can change the decomposition course of macromolecular material, fire-retardant in condensed phase.Three element cooperative flame retardants can produce
Excellent flame retardant effect.Fire retardant efficiency of the present invention is high, becomes charcoal effect good, and applied range has good DEVELOPMENT PROSPECT.
Content of the invention
An object of the present invention is to propose a kind of silicon, phosphorus, the double -1- sulfenyl of sulfur cooperative flame retardant carbon forming agent dimethyl silicic acid
Phospha -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl compound, its flame-retarded efficiency is high, can overcome of the prior art
Not enough.
For achieving the above object, present invention employs following technical scheme：
Double -1- sulfenyl phospha -2 of dimethyl silicic acid, 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl compound, it is special
Levy and be, the structure of this compound is shown below：
Another object of the present invention is to proposing a kind of silicon, phosphorus, the double -1- sulfenyl phosphorus of sulfur synergistic fire retardant dimethyl silicic acid
Miscellaneous -2, the preparation method of 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl compound, its process is simple, equipment investment is few,
It is easy to large-scale production, and raw material is cheap and easy to get, with low cost, the method is：
In the reactor equipped with agitator, thermometer and fractionating device, logical nitrogen displacement air, at 25 DEG C of temperature,
Add a certain amount of 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane, dimethylformamide dimethyl epoxide silicon
Alkane and volume milliliter number, with respect to the organic solvent of 5～15 times of dimethyldimethoxysil,ne quality grams, are warming up to backflow, body
The reflux temperature of system raises with the carrying out of reaction, is eventually held in 80 DEG C～100 DEG C, and 5h～9h is reacted in fractional distillation, controls and divides
Evaporate not higher than 65 DEG C of column top temperature, after the methanol fractionating out generation reaches theoretical amount, reaction completes, and is cooled to 25 DEG C, sucking filtration, use
The methanol of product theory quality grams 1-2 times volume milliliter number or washing with alcohol, sucking filtration, it is dried, obtain white solid powder diformazan
Double -1- sulfenyl phospha -2 of base silicic acid, 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester.
The method can be also：
In the reactor equipped with agitator, thermometer and hydrogen chloride absorption device, catch up with most air with nitrogen, in temperature 25
At DEG C, add a certain amount of 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane and volume milliliter number
With respect to 5～15 times of organic solvent of dimethyldichlorosilane quality grams, it is slowly added dropwise dimethyldichlorosilane, with Deca speed
Not higher than 40 DEG C of degree controlling reaction temperature, reacts 5h～10h at 40 DEG C～80 DEG C after dripping off；After hydrogen chloride discharges, react
Become, be cooled to 25 DEG C, sucking filtration, with methanol or the washing with alcohol of product theory quality grams 1-2 times volume milliliter number, it is dried, obtains
Double -1- sulfenyl phospha -2 of white solid powder dimethyl silicic acid, 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester.
A certain amount of 1- sulfenyl phospha -4- methylol -2 as above, 6,7- trioxa-l-phosphabicyclos [2.2.2] octane is two
Methyl dimethoxysilane or dimethyldichlorosilane：1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos [2.2.2]
The mol ratio of octane is 1: 2～1: 4.
Organic solvent as above is acetonitrile, glycol dimethyl ether or dioxane.
Double -1- sulfenyl phospha -2 of the dimethyl silicic acid of the present invention, 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester is
White solid powder, product yield is 87.3%～94.5%, and fusing point is 164 ± 2 DEG C, and decomposition temperature is 270 ± 5 DEG C.It is fitted
Share the fire-retardant carbon forming agent making the materials such as polyester, polyurethane, epoxy resin, unsaturated-resin.Double -1- the sulfenyl of this dimethyl silicic acid
Phospha -2, the preparation technology principle of 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester is shown below：
Compared with prior art, the beneficial effects of the present invention is：
1. double -1- sulfenyl phospha -2 of dimethyl silicic acid of the present invention, 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester contains
Silicon, phosphorus, three kinds of ignition-proof elements of sulfur, its cooperative flame retardant efficiency is high, and element silicon has into charcoal effect, can effectively prevent material to be subject to hot melt
The second-time burning melted drippage and produce, P elements can generate polyphosphoric acid film in burning, blocks combustible and air, element sulphur energy
Change the decomposition course of macromolecular material, condensed phase is fire-retardant.
2. double -1- sulfenyl phospha -2 of dimethyl silicic acid of the present invention, 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester is tied
There is in structure C-Si key, be organosilicon structures, organosilicon structures good stability, resistance to water are strong, are more easily generated densification during burning
Charcoal-silicon layer, flame retardant effect is more excellent.
3. double -1- sulfenyl phospha -2 of dimethyl silicic acid of the present invention, 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester pair
Title property is good, physical and chemical performance is stable, good with the macromolecular material compatibility, and decomposition temperature is high, adapts to the high temperature of engineering material
Processing.
4. double -1- sulfenyl phospha -2 of dimethyl silicic acid of the present invention, 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester
Preparation method process is simple, need not add catalyst and not introduce impurity, and equipment is simple, with low cost, is suitable to large-scale production, has
Application and development prospect well.
Brief description
Structure and performance spy in order to further illustrate product provide drawings described below.
Fig. 1 is double -1- sulfenyl phospha -2 of dimethyl silicic acid, 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester infrared
Spectrogram；Fig. 1 shows, 971cm-1Locate the stretching vibration peak for P-O key, 2968cm-1、2904cm-1Place is methyl and methylene
The stretching vibration peak of C-H, 693cm-1Locate the characteristic absorption peak for P=S, 1026cm-1Locate the stretching vibration peak for C-O key,
802cm-1Locate the stretching vibration peak for Si-C key, 1103cm-1Locate the characteristic absorption peak for Si-O-C key.
Fig. 2 is double -1- sulfenyl phospha -2 of dimethyl silicic acid, the nuclear-magnetism of 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester
Spectrogram；Fig. 2 shows, makees solvent with deuterated dimethyl sulfoxide, for C (CH at δ 4.58-4.612O on the methylene being connected with oxygen on)
Hydrogen peak；For CCH at δ 3.50-3.532Hydrogen peak on the methylene that OSi is connected with oxygen, for CH at δ 0.06-0.093Si is connected with oxygen
Hydrogen peak on methylene, is water peak at δ 3.35, the proton peak exchanging for solvent deuterated dimethyl sulfoxide at δ 2.51.
Fig. 3 is double -1- sulfenyl phospha -2 of dimethyl silicic acid, the thermogravimetric of 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester
Figure；Fig. 3 shows, product starts slow weightlessness when 120 DEG C, caused by this is likely due to the moisture in absorption air；Work as intensification
Start weightlessness to product when 260 DEG C about；When being warming up to 270 DEG C, weight loss rate reaches peak value, and now weightless about 27%；When
Temperature to 700 DEG C, now has about 36% surplus charcoal rate.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
, in tetra- mouthfuls of reaction bulbs of the 250ml equipped with agitator, thermometer and fractionating device, logical nitrogen displacement is empty for embodiment 1
Gas, at a temperature of 25 DEG C, adds 21.56g (0.11mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos
[2.2.2] octane, 6.01g (0.05mol) dimethyldimethoxysil,ne and 50mL dioxane, are warming up to backflow, system is returned
The temperature of stream carries out and raises with reaction, is eventually held in 95 DEG C of fractional distillation reaction 7h, controls fractional distillation column top temperature to be not higher than 65
DEG C, after the methanol fractionating out generation reaches theoretical amount, reaction completes, and is cooled to 25 DEG C, sucking filtration, and 25mL dehydrated alcohol used again by filter cake
Washing, sucking filtration, it is dried, obtain double -1- sulfenyl phospha -2 of white solid powder dimethyl silicic acid, 6,7- trioxa-l-phosphabicyclos [2.2.2]
Octyl group -4- methyl ester, yield is 90.1%.
, in tetra- mouthfuls of reaction bulbs of the 250ml equipped with agitator, thermometer and fractionating device, logical nitrogen displacement is empty for embodiment 2
Gas, at a temperature of 25 DEG C, adds 39.23g (0.20mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos
[2.2.2] octane, 6.01g (0.05mol) dimethyldimethoxysil,ne and 100mL glycol dimethyl ether, are warming up to backflow, body
Temperature the carrying out and raise with reaction of system's backflow, is eventually held in 80 DEG C of fractional distillation reaction 9h, controls fractional distillation column top temperature not high
In 65 DEG C, after the methanol fractionating out generation reaches theoretical amount, reaction completes, and is cooled to 25 DEG C, sucking filtration, and 40mL methanol used again by filter cake
Washing, sucking filtration, it is dried, obtain double -1- sulfenyl phospha -2 of white solid powder dimethyl silicic acid, 6,7- trioxa-l-phosphabicyclos [2.2.2]
Octyl group -4- methyl ester, yield is 89.6%.
, in tetra- mouthfuls of reaction bulbs of the 250ml equipped with agitator, thermometer and fractionating device, logical nitrogen displacement is empty for embodiment 3
Gas, at a temperature of 25 DEG C, adds 19.62g (0.10mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos
[2.2.2] octane, 6.01g (0.05mol) dimethyldimethoxysil,ne and 30mL dioxane, are warming up to backflow, system is returned
The temperature of stream carries out and raises with reaction, is eventually held in 100 DEG C of fractional distillation reaction 5h, controls fractional distillation column top temperature to be not higher than 65
DEG C, after the methanol fractionating out generation reaches theoretical amount, reaction completes, and is cooled to 25 DEG C, sucking filtration, and 35mL dehydrated alcohol used again by filter cake
Washing, sucking filtration, it is dried, obtain double -1- sulfenyl phospha -2 of white solid powder dimethyl silicic acid, 6,7- trioxa-l-phosphabicyclos [2.2.2]
Octyl group -4- methyl ester, yield is 87.3%.
, in tetra- mouthfuls of reaction bulbs of the 250ml equipped with agitator, thermometer and fractionating device, logical nitrogen displacement is empty for embodiment 4
Gas, at a temperature of 25 DEG C, adds 29.43g (0.15mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos
[2.2.2] octane, 6.01g (0.05mol) dimethyldimethoxysil,ne and 80mL dioxane, are warming up to backflow, system is returned
The temperature of stream carries out and raises with reaction, is eventually held in 100 DEG C of fractional distillation reaction 6h, controls fractional distillation column top temperature to be not higher than 65
DEG C, after the methanol fractionating out generation reaches theoretical amount, reaction completes, and is cooled to 25 DEG C, sucking filtration, and 45mL dehydrated alcohol used again by filter cake
Washing, sucking filtration, it is dried, obtain double -1- sulfenyl phospha -2 of white solid powder dimethyl silicic acid, 6,7- trioxa-l-phosphabicyclos [2.2.2]
Octyl group -4- methyl ester, yield is 91.2%.
Embodiment 5 in tetra- mouthfuls of reaction bulbs of the 250ml equipped with agitator, thermometer and hydrogen chloride absorption device, catch up with by nitrogen
Air to the greatest extent in bottle, at a temperature of 25 DEG C, adds 23.54g (0.12mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxas
Bicyclic [2.2.2] octane and 60mL acetonitrile, are slowly added dropwise 6.45g (0.05mol) dimethyldichlorosilane, with rate of addition control
Not higher than 40 DEG C of reaction temperature, reacts 8h after dripping off, after hydrogen chloride discharges, reaction completes, and is cooled to 25 DEG C at 60 DEG C；Take out
Filter, 40mL washing with alcohol use again by filter cake, sucking filtration, is dried, and obtains white solid powder dimethyl silicic acid pair -1- sulfenyl phospha -2, and 6,
7- trioxa-l-phosphabicyclo [2.2.2] octyl group -4- methyl ester, yield is 92.4%.
Embodiment 6 in tetra- mouthfuls of reaction bulbs of the 250ml equipped with agitator, thermometer and hydrogen chloride absorption device, catch up with by nitrogen
Air to the greatest extent in bottle, at a temperature of 25 DEG C, adds 19.62g (0.10mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxas
Bicyclic [2.2.2] octane and 35mL dioxane, are slowly added dropwise 6.45g (0.05mol) dimethyldichlorosilane, with rate of addition
Not higher than 40 DEG C of controlling reaction temperature, reacts 6h after dripping off, after hydrogen chloride discharges, reaction completes at 80 DEG C；It is cooled to 25 DEG C,
Sucking filtration, filter cake is washed with 30mL methanol again, sucking filtration, is dried, and obtains double -1- sulfenyl phospha -2 of white solid powder dimethyl silicic acid,
6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester, yield is 91.3%.
Embodiment 7 in tetra- mouthfuls of reaction bulbs of the 250ml equipped with agitator, thermometer and hydrogen chloride absorption device, catch up with by nitrogen
Air to the greatest extent in bottle, at a temperature of 25 DEG C, adds 35.30g (0.18mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxas
Bicyclic [2.2.2] octane and 120mL glycol dimethyl ether, are slowly added dropwise 6.45g (0.05mol) dimethyldichlorosilane, to drip
Not higher than 40 DEG C of Acceleration Control reaction temperature, reacts 10h after dripping off, after hydrogen chloride discharges, reaction completes at 40 DEG C；Cooling
To 25 DEG C, sucking filtration, filter cake uses 50mL ethanol to pull an oar again, and sucking filtration is dried, and obtains the double -1- sulfenyl of white solid powder dimethyl silicic acid
Phospha -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester, yield is 93.3%.
Embodiment 8 in tetra- mouthfuls of reaction bulbs of the 250ml equipped with agitator, thermometer and hydrogen chloride absorption device, catch up with by nitrogen
Air to the greatest extent in bottle, at a temperature of 25 DEG C, adds 29.43g (0.15mol) 1- sulfenyl phospha -4- methylol -2,6,7- trioxas
Bicyclic [2.2.2] octane and 50mL dioxane, are slowly added dropwise 6.45g (0.05mol) dimethyldichlorosilane, with rate of addition
Not higher than 40 DEG C of controlling reaction temperature, reacts 5h after dripping off, after hydrogen chloride discharges, reaction completes at 80 DEG C；It is cooled to 25 DEG C,
Sucking filtration, filter cake is washed with 40mL methanol again, sucking filtration, is dried, and obtains double -1- sulfenyl phospha -2 of white solid powder dimethyl silicic acid,
6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester, yield is 94.5%.
Inventor is by double for the dimethyl silicic acid of above-mentioned preparation -1- sulfenyl phospha -2,6,7- trioxa-l-phosphabicyclos [2.2.2]
Octyl group -4- methyl ester (DMSSPE) individually or carries out composite usage in fire-retardant poly- terephthaldehyde with melamine polyphosphate (MPP)
In sour butanediol ester (PBT).Reference：GB/T2406-2008《Plastics Combustion method for testing performance-oxygen index method》The pole of test sample bar
Limited oxygen index (LOI).DMSSPE is taken to mix homogeneously in varing proportions with PBT or take DMSSPE, MPP and PBT to mix in varing proportions
Close uniformly, with extruder extrusion, make the batten of a diameter of 3mm, and its fire-retardant melt-dropping property is tested, list portion
Separating tests result is as shown in table 1～2：
The fire resistance data of the independent flame-retardant PBT of table 1 DMSSPE
| Sequence | Addition/% | LOI/% | Molten drop situation | Become charcoal situation |
| 1 | 0 | 21 | Drippage | Do not become charcoal |
| 2 | 10 | 24 | Do not drip | Become charcoal |
| 3 | 20 | 29 | Do not drip | Become charcoal |
| 4 | 30 | 33 | Do not drip | Become charcoal |
Table 1 shows, when individually the addition in PBT reaches 10% to DMSSPE, PBT just can become charcoal not drip in burning
Fall；After addition reaches 20%, the LOI of PBT reaches 29%, reaches fire retardant rank.This can be seen that DMSSPE has to PBT
Good fire-retardant one-tenth charcoal effect.
The fire resistance data of table 2 DMSSPE and MPP compositional flame-retardant PBT
Table 2 shows, when the addition total amount that DMSSPE and MPP is compounded in PBT is 20%, DMSSPE and MPP mass
During for 1: 1, the LOI of PBT is up to 34% to ratio, and can become rapidly charcoal, effectively prevents melting drippage.As can be seen here, DMSSPE and MPP
Composite usage has good synergetic in PBT.
Claims (5)
1. a kind of silicon, phosphorus, double -1- sulfenyl phospha -2 of sulphur element cooperative flame retardant carbon forming agent dimethyl silicic acid, 6,7- trioxas are double
Ring [2.2.2] octyl group -4- methyl compound is it is characterised in that the structure of this compound is shown below：
2. double -1- sulfenyl phospha -2 of dimethyl silicic acid according to claim 1,6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -
The preparation method of 4- methyl ester is it is characterised in that the method is：
In the reactor equipped with agitator, thermometer and fractionating device, logical nitrogen displacement air, at 25 DEG C of temperature, add
A certain amount of 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane, dimethyldimethoxysil,ne and
Volume milliliter number, with respect to the organic solvent of 5～15 times of dimethyldimethoxysil,ne quality grams, is warming up to backflow, system
Reflux temperature raises with the carrying out of reaction, is eventually held in 80 DEG C～100 DEG C, and 5h～9h is reacted in fractional distillation, controls dephlegmator
Not higher than 65 DEG C of top temperature, after the methanol fractionating out reaches theoretical amount, reaction completes, and is cooled to 25 DEG C, and sucking filtration uses product theory
The methanol of quality grams 1-2 times volume milliliter number or washing with alcohol, sucking filtration, be dried, obtain white solid powder dimethyl silicic acid double-
1- sulfenyl phospha -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester.
3. double -1- sulfenyl phospha -2 of dimethyl silicic acid according to claim 1,6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -
The preparation method of 4- methyl ester is it is characterised in that the method is：
In the reactor equipped with agitator, thermometer and hydrogen chloride absorption device, catch up with most air with nitrogen, in 25 DEG C of temperature
Under, add a certain amount of 1- sulfenyl phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane and volume milliliter number phase
For 5～15 times of organic solvent of dimethyldichlorosilane quality grams, it is slowly added dropwise dimethyldichlorosilane, with rate of addition
Not higher than 40 DEG C of controlling reaction temperature, reacts 5h～10h at 40 DEG C～80 DEG C after dripping off；After hydrogen chloride discharges, reaction completes,
It is cooled to 25 DEG C, sucking filtration, with methanol or the washing with alcohol of product theory quality grams 1-2 times volume milliliter number, it is dried, obtains white
Double -1- sulfenyl phospha -2 of pressed powder dimethyl silicic acid, 6,7- trioxa-l-phosphabicyclos [2.2.2] octyl group -4- methyl ester.
4. double -1- sulfenyl phospha -2 of dimethyl silicic acid according to Claims 2 or 3,6,7- trioxa-l-phosphabicyclos [2.2.2] are pungent
The preparation method of base -4- methyl ester it is characterised in that a certain amount of 1- sulfenyl phospha -4- methylol -2 as above, 6,7- tri-
Oxabicyclo [2.2.2] octane is dimethyldimethoxysil,ne or dimethyldichlorosilane: 1- sulfenyl phospha -4- methylol -
The mol ratio of 2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane is 1: 2～1: 4.
5. double -1- sulfenyl phospha -2 of dimethyl silicic acid according to Claims 2 or 3,6,7- trioxa-l-phosphabicyclos [2.2.2] are pungent
The preparation method of base -4- methyl ester is it is characterised in that organic solvent as above is acetonitrile, glycol dimethyl ether or dioxy six
Ring.
Priority Applications (1)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279873A (en) * | 2020-10-27 | 2021-01-29 | 苏州科技大学 | Reactive flame retardant vinyl organosilicon caged phosphorothioate compound, and preparation method and application thereof |
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| CN103992351A (en) * | 2014-06-11 | 2014-08-20 | 苏州科技学院相城研究院 | Preparation method of dimethylsilyl dioxyl bi-cage ring phosphate |
| CN104004022A (en) * | 2014-06-11 | 2014-08-27 | 苏州科技学院相城研究院 | Caged bicyclic flame-retardant charring agent dimethyl silicic acid PEPA ester compound and preparation method thereof |
| CN106167505A (en) * | 2016-07-04 | 2016-11-30 | 华北理工大学 | A kind of siliceous caged thiophosphate fire retardant and preparation method thereof |
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| CN103992351A (en) * | 2014-06-11 | 2014-08-20 | 苏州科技学院相城研究院 | Preparation method of dimethylsilyl dioxyl bi-cage ring phosphate |
| CN104004022A (en) * | 2014-06-11 | 2014-08-27 | 苏州科技学院相城研究院 | Caged bicyclic flame-retardant charring agent dimethyl silicic acid PEPA ester compound and preparation method thereof |
| CN106167505A (en) * | 2016-07-04 | 2016-11-30 | 华北理工大学 | A kind of siliceous caged thiophosphate fire retardant and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112279873A (en) * | 2020-10-27 | 2021-01-29 | 苏州科技大学 | Reactive flame retardant vinyl organosilicon caged phosphorothioate compound, and preparation method and application thereof |
| CN112279873B (en) * | 2020-10-27 | 2024-04-16 | 苏州科技大学 | Reactive flame retardant vinyl organosilicon cage-shaped phosphorothioate compound and preparation method and application thereof |
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